Revisiting Reaction Mechanism of Regioselective Disulfide-Catalyzed Photocatalytic Aerobic Oxidative Cleavage of 1-Arylbutadienes: A Computational Study

Fıstıkçı M., LAFZİ F., EŞSİZ S.

ChemPhysChem, cilt.26, sa.11, 2025 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 26 Sayı: 11
  • Basım Tarihi: 2025
  • Doi Numarası: 10.1002/cphc.202401004
  • Dergi Adı: ChemPhysChem
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus, PASCAL, Biotechnology Research Abstracts, Chemical Abstracts Core, Chimica, Compendex, EMBASE, INSPEC, MEDLINE
  • Anahtar Kelimeler: aerobic oxidative cleavage, arylbutadienes, density functional theory, diaryl disulfides, DLPNO-CCSD(T)
  • Hakkari Üniversitesi Adresli: Evet

Özet

A computational study of the regioselective aerobic oxidative cleavage of 1-arylbutadienes is carried out employing density functional theory and high-level coupled-cluster methods, such as coupled-cluster singles and doubles with perturbative triples [CCSD(T)]. The results demonstrate that the reaction proceeds either via the intramolecular reduction or dimerization of peroxyl radical. These findings are in contrast to a previously proposed mechanism that progresses via formation of the dioxetane ring. The computations further indicate that the homolysis of S-S bond of diaryl disulfide derivatives cannot be achieved by irradiation with direct visible light under the reaction conditions due to the high bond dissociation energy.